Phenoxarsine compounds incorporated into resins with phenols

ABSTRACT

.Iadd.Microbicidal properties are imparted to vinyl resins by the incorporation therein of a selected phenoxarsine compound dissolved in a solvent which may be one of a selected group of phenols and monocarboxylic acids. .Iaddend.

This invention relates to vinyl resins having bactericidal properties.More particularly, it relates to polyvinyl esters which display markedanti-bacterial and anti-fungal characteristics. Still more particularly,it relates to molded vinyl resins and to plasticizers therefor and to anovel method of incorporating phenoxarsine compounds as a component ofthe plasticizers.

In accordance with the invention, a solution of a phenoxarsine isprepared, the solution is introduced into a compatible plasticizer andthe plasticizer composition incorporated into vinyl resins which will besubjected to mechanical manipulation, i.e., to pressing, swaging,molding, etc., to produce molded objects, flexible sheeting and film,coating compositions, and the like.

In general, resinous materials such as polymers and copolymers ofpolyvinyl esters are inert to microbial and fungal attack. Nevertheless,they readily act as carriers for microorganisms and the surface ofresinous articles may become contaminated with materials which functionas nutrients for the microorganisms so that the growth of the latter canoccur on such surfaces. In addition to being a continuous source ofcontamination, the articles themselves are often subject todeterioration due to bacterial and fungal attack on the plasticizersincorporated into the resins to impart certain desirable physicalproperties and to facilitate molding operations.

It has been common practice, in order to protect resins from bacterialand fungal deterioration to incorporate agents for the purpose ofrendering the resinous products bacteriostatic. Most of these agentshave suffered from the disadvantage that their solubility in the resinsor in the plasticizers were limited, or they were relatively fugitive,as a consequence of which their effectiveness was of limited duration. Afurther disadvantage has been that the known agents must be used inrelatively large concentrations, as for example, 2% to 4% of the resin.This is ordinarily objectionable both from the viewpoint of cost andbecause the excessive amount of bacteriostat may adversely affect thecolor or the physical properties of the resin. The method ofincorporating the agents capable of imparting bactericidal andfungicidal properties, used hereto, has been to mill in, for example,powdered fungicidal agent or to mix in the resin being compounded, asolution of the agent in such compatible fugitive solvents as toluene,benzene, and the like.

Now, it has been discovered that phenoxarsine compounds which areinsoluble in the fugitive solvents commonly available in the plasticindustry, for example, glycols such as propylene glycol, ethers such asethylene glycol monobutyl ether, ketones such as ethyl methyl ketone,diisobutyl ketone, etc., and the like and also insoluble in plasticizerssuch as, dioctyl phosphate, tricresyl phosphate, epoxidized tallate,butyl phthalyl butyl glycolate, ethyl salicylate, and the like, can beincorporated in effective small amounts in a unique solution formcompatible with the plasticizers to provide the compositions withexcellent anti-bacterial and anti-fungal properties. The phenoxarsinecompounds when incorporated by this phenol solvent solution methoddisplay an effective microbicidal and fungicidal action rather than amere inhibition of the growth of such bacteria.

As above indicated, relatively small amounts of the phenoxarsinecomponent, i.e., amounts of the order of 100 to 500 parts per million,present in the resinous compositions in a solution form are effective toproduce the desired effect.

The phenoxarsine compounds to be employed in accordance with the presentinvention have the following general formula: ##STR1##

Derivatives of the phenoxarsines useful in the instant invention are,for example, the halogen derivatives such as 10-chlorophenoxarsine,10-iodo-phenoxarsine, 10-bromo-phenoxarsine,4-methyl-10-chlorophenoxarsine, 2-tertiary butyl-10-chlorophenoxarsine,1,4-dimethyl-10-chlorophenoxarsine, 2-methyl-8,10-dichloro phenoxarsine,1,3,10-trichloro phenoxarsine, 2,6,10-trichloro phenoxarsine,2,8,10-trichloro phenoxarsine, 1,2,4,10-tetrachloro phenoxarsine, theoxygen derivatives such as the 10,10'-oxybis phenoxarsine, the thioderivatives such as 10-thiocyanato phenoxarsine, 10,10'-thio bisphenoxarsine, also may be used.

These phenoxarsine compounds are prepared for incorporation into aplasticizer and subsequent incorporation into the resins by dissolvingin hydroxy-bearing solvents in which the compounds are soluble to theextent of at least 5%. Generally, the phenoxarsines have a highersolubility in compounds such as phenols and the combination ofphenoxarsine and the phenols are preferred because quantities ofphenoxarsines of the order of 300 to 500 parts per million areobtainable with lesser quantities of the solvent phenols which phenolscannot be tolerated in, for example, vinyl resins in too great aproportion.

Materials useful as a solvent for the phenoxarsine compounds are thosehaving a labile hydroxyl group. Useful compounds are mono and di-hydroxycompounds, for example, phenol, phenol derivatives, for example, thealkyl phenols, such as cresols, e.g., methyl phenol,2-methyl-5-isopropyl phenol, 3-methyl-6-isopropyl phenol, and the like.Chlorinated phenols such as 4-chloro-2-phenylphenol, and6-chloro-2-phenylphenol. Amino phenols such as p-aminophenol andm-aminophenol. Dihydric phenols such as catechol, resorcinol, 3,5,dihydric toluene, and the like, aliphatic alcohols having 5 to 12 carbonatoms such as lauric, 2-ethyl hexanol, octenol, 1,2,6-hexantriol,2-methoxy methyl-2,4, dimethyl pentane diol, and the like, andmonocarbocyclic acid having 5 to 12 carbon atoms such as caproic acid,2-ethyl hexoic acid, isotoic acid, and the like. The solvent carriercompatible with the plasticizers which is preferred, is a non-toxicalkyl phenol, such as nonyl phenol, dodecyl phenol, di-sec amyl phenol,and the like.

The solution of phenoxarsine in a solvent containing a labile hydroxylgroup is incorporated into a plasticizer for the resin to bemechanically worked. Typical plasticizers are tricresyl phosphate,dipropylene glycol, dibenzoate, diphenylcresyl phosphate, epoxidizedsoya, epoxidized tallate, dioctyl azelate, alkyl aryl phosphates,diisobutyl phthalate, hydrogenated methyl rosin ester, and the like.

The solvent solutions of phenoxarsine which are preferred, are thosewhich hold in stable solution between about 10% and about 25% by weightof arsenical although amounts of arsenical as low as 5% may be used.Such a solution can be dissolved and/or dispersed in the plasticizer inamounts constituting between about 2% and about 10% by weight of thetotal mixture, with amounts in the range between about 4% and about 6%preferred. The plasticizer compositions thus contain between about 0.2%and 2.5% of phenoxarsine compound, between about 1.8% and 7.5% ofsolvent and between about 90% to 98% of plasticizer.

When phenoxarsines are present in a plasticizer in the quantity setforth, the phenoxarsine content of a processed resin, for example, vinylresin, will be in the range between about 0.02% and about 0.1%, i.e.,amounts in the range between about 200 and 1000 parts per million.

In order to more fully illustrate the invention, the following examplesare included. These examples are intended to be illustrative and aregiven without any intention that the invention be limited thereto.

.[.Example I.].

.[.A solution indicated solution A was prepared by mixing 20 parts byweight of 10-chlorophenoxarsine into 80 parts by weight of nonyl phenol.The mixture was heated to approximately 230° F. to attain a temperaturesufficient to melt the 10-chlorophenoxarsene. After agitation until auniform solution was attained, the solution was cooled to roomtemperature..].

.Badd..[.100 parts of the phenol solution was then mixed with 1900 partsby weight of expoxidized soya..]..Baddend.

.[.A plastisol was prepared from the phenol solution containingepoxidized soya which has the following formulation: 1000 partspolyvinyl chloride resin (Geon 121), 435 parts of dioctyl azelateplasticizer, 50 parts of solution A and 15 parts barium-cadmium-zincsoap. The liquid ingredients were mixed and then the solid resin addedslowly with agitation. After thorough admixture, the resin was molded toa film of approximately 100 mils thickness and heated for 10 minutes at350° F. to effect a cure..].

.[.The vinyl film was cut into test rectangles, placed on a glass panelso that there was one for each five minutes of test period. The glasspanels with the samples were placed in an oven which was maintained at atemperature of 375° F. At each five minute interval, one piece of filmwas removed up to a total of 60 minutes. The vinyl test rectanglesshowed that the yellowing of the film containing the phenol solution(solution A) was equal to or less than control films containing nophenol solution..].

.[.Test panels were also cut from the vinyl film and subjected to thefollowing test to establish fungicidal activity..].

.[.Test panels were placed on nutrient agar surfaces in petri dishes,each agar surface having been previously inoculated with a selectedmicroorganism. The petri dishes were covered and incubated for a periodof 14 days for fungi at a temperature of 30° C., and for 34 hours at atemperature of 37° C., for bacteria. At the end of this period, theclear zone indicating inhibition of growth extending outwardly from thetest panels was measured. The results are given below in Table I.

                  Table I                                                         ______________________________________                                                                    Zone of                                                                       inhibi-                                                                       tion                                                                 Organism (mm.)                                             ______________________________________                                        Panel containing 5% phenol solution                                                                       A. niger                                                                              15                                        (500 p.p.m. arsine compound)                                                                             S. aureus                                                                              12                                        Control panel containing no micro-biocide                                                                A. niger  0                                                                   S. aureus                                                                               0.].                                     ______________________________________                                    

EXAMPLE .[.II.].

A solution indicated solution B was prepared by mixing 20 parts byweight of 10,10'-oxybis phenoxarsine into 80 parts by weight ofdi-secondary amyl phenol. The mixture was heated to approximately 230°F. to attain a temperature sufficient to melt the 10,10'-oxybisphenoxarsine. After agitation until a uniform solution was attained, thesolution was cooled to room temperature.

100 parts of the phenol solution was then mixed with 1900 parts byweight of epoxidized soya.

A plastisol was prepared from the phenol solution having the followingformulation, 1000 parts polyvinyl chloride resin (Geon 121), 435 partsof dioctyl azelate plasticizer, 50 parts of solution B and 15 partsbarium-cadmium-zinc soap. The liquid ingredients were mixed and then thesolid resin added slowly with agitation. After thorough admixture, theresin was molded to a film of approximately 100 mil thickness and heatedfor 10 minutes at 350° F. to effect a cure.

The vinyl film was cut into test rectangles, placed on a glass panel sothat there was one for each five minutes of test period. The glasspanels with the samples were placed in an oven which was maintained at atemperature of 375° F. At each five minute interval, one piece of filmwas removed up to a total of 60 minutes. The vinyl test rectanglesshowed that the yellowing of the film containing the phenol solution(solution A) was equal to or less than control films containing nophenol solution.

.[.Test panels were also cut from the vinyl film and subjected to thetest to establish fugicidal activity as described in Example I..]..Iadd.

Test panels were also cut from the vinyl film and subjected to thefollowing test to establish fungicidal activity.

Test panels were placed on nutrient agar surfaces in petri dishes, eachagar surface having been previously inoculated with a selectedmicroorganism. The petri dishes were covered and incubated for a periodof 14 days for fungi at a temperature of 30° C., and for 34 hours at atemperate of 37° C., for bacteria. At the end of this period, the clearzone indicating inhibition of growth extending outwardly from the testpanels was measured. The results are given below in the Table. .Iaddend.

                  TABLE .[.II.].                                                  ______________________________________                                                                    Zone of                                                                       Inhibi-                                                                       tion                                                                 Organism (mm.)                                             ______________________________________                                        Panel containing 5% phenol solution                                                                       A. niger                                                                              15                                        (500 p.p.m. arsine compound).                                                                            S. aureus                                                                              12                                        Control panel containing no micro-biocide                                                                A. niger  0                                                                   S. aureus                                                                               0                                        ______________________________________                                    

The foregoing description is given for clearness and understanding onlyand no unnecessary limitations should be understood therefor, formodifications will be obvious to those skilled in the art.

I claim: .[.1. A method of incorporating microbicidal amounts ofphenoxarsine compounds into vinyl resin material which comprisesdissolving a phenoxarsine compound selected from the group consisting of10-halophenoxarsines, alkyl substituted 10-halophenoxarsines, halogensubstituted 10-halophenoxarsines and derivatives of phenoxarsineswherein said derivatives are selected from the group consisting of10,10'-oxybis phenoxarsine, 10-thiocyanato phenoxarsine and10,10'-thiobis phenoxarsine, in a solvent selected from the groupconsisting of phenol, alkyl phenols, chlorinated phenols, amino phenols,dihydric phenols, aliphatic alcohols having 5 to 12 carbon atoms andmonocarbocyclic acids having 5 to 12 carbon atoms, admixing said solventsolution with said vinyl resin material and processing said admixture todesired solid physical form..]. . A method according to claim .[.1.]..Iadd.11 .Iaddend.wherein the phenoxarsine compound is10-chlorophenoxarsine.
 3. A method according to claim .[.1.]. .Iadd.11.Iaddend.wherein the solvent is nonyl phenol.
 4. A composition of matteruseful for plasticizing vinyl resins and imparting microbicidalproperties thereto which comprises a liquid plasticizer for vinyl resinsand a microbicidal amount of a phenoxarsine compound selected from thegroup consisting of 10-halophenoxarsines, alkyl substituted10-halophenoxarsines, halogen substituted .Iadd.10-halophenoxarsines.Iaddend.and derivatives of phenoxarsines wherein said derivatives areselected from the group consisting of 10,10'-oxybis phenoxarsine,10-thiocyanato phenoxarsine and 10,10'-thiobis phenoxarsine, saidphenoxarsine compound being present in the plasticizer in the form ofsolute in a solvent selected from the group consisting of phenol, alkylphenols, chlorinated phenols, amino phenols, dihydric phenols, aliphaticalcohols having 5 to 12 carbon atoms and monocarbocyclic acids having 5to 12 carbon atoms, said solvent and solute being uniformly distributedin said plasticizer to form a single phase system.
 5. A compositionaccording to claim 4 wherein the phenoxarsine compound is present in theform of the solute in a nonyl phenol solution.
 6. A compositionaccording to claim 4 wherein the phenoxarsine is present in the form ofthe solute in a mixture of disecondary amyl phenol and nonyl phenol. 7.A composition of matter comprising a uniform admixture of vinyl resinand a vinyl resin plasticizer containing a microbicidal amount of aphenoxarsine compound selected from the group consisting of10-halophenoxarsines, alkyl substituted 10-halophenoxarsines, halogensubstituted .Iadd.10-halophenoxarsines .Iaddend.and derivatives ofphenoxarsines wherein said derivatives are selected from the groupconsisting of 10,10'-oxybis phenoxarsine, 10-thiocyanato phenoxarsineand 10,10'thiobis phenoxarsine present in said plasticizer as the solutein a solvent selected from the group consisting of phenol, alkylphenols, chlorinated phenols, amino phenols, dihydric phenols, aliphaticalcohols having 5 to 12 carbon atoms and monocarbocyclic acids having 5to 12 carbon atoms, said solvent and solute being uniformly distributedin said plasticizer to form a single phase system.
 8. A composition ofmatter comprising a uniform mixture of approximately 1000 parts byweight of liquid polyvinyl chloride resin, 435 parts by weight ofdioctyl azelate, 0.5 parts by weight of 10,10'-oxybis phenoxarsine, 2parts by weight of nonyl phenol, 47.5 parts of epoxidized soya, 15 partsby weight of barium-cadmium-zinc soap, said 10,10'-oxybis phenoxarsinebeing present as a solute in the nonyl phenol solution which isuniformly distributed in said epoxidized soya forming a single phasesystem.
 9. A method according to claim .[.1.]. .Iadd.11 .Iaddend.inwhich the solvent solution of phenoxarsine is distributed uniformly in aplasticizer for vinyl resins to form a single phase system prior toadmixing with vinyl resin material.
 10. The method according to claim 9in which the resultant solution produced by the uniform distribution ofa phenoxarsine compound in a plasticizer for vinyl resins, is mixed withsoap and liquid vinyl resin to form a plastisol and the plastisol thenprocessed to desired physical form. .Iadd.
 11. A method of incorporatingmicrobicidal amounts of phenoxarsine compounds into vinyl resin materialwhich comprises dissolving a phenoxarsine compound selected from thegroup consistng of 10-halophenoxarsines, alkyl substituted10-halophenoxarsines, halogen substituted 10-halophenoxarsines andderivatives of phenoxarsines wherein said derivatives of selected fromthe group consisting of 10,10'-oxybis phenoxarsine, 10-thiocycanatophenoxarsine and 10,10'-thiobis phenoxarsine, in a solvent selected fromthe group consisting of phenol, alkyl phenols, chlorinated phenols,amino phenols, dihydric phenols, aliphatic alcohols having 5 to 12carbon atoms and monocarbocyclic acids having 5 to 12 carbon atoms,admixing said solvent solution with said vinyl resin material in anamount to provide a microbicidal amount of said phenoxarsine compound insaid vinyl resin material and processing said admixture to desired solidphysical form. .Iaddend.